Oxyalkylated polyepoxide-treated amine-modified thermoplastic phenol aldehyde resins, and method of making same



United States Patent OXYALKYLATED POLYEPOXIDE -TREATED AMINE-MODIFIED THERMOPLASTIC PHENOL .ALDEHYDE RESINS, AND METHOD OF MAK- ING SAME Melvin De Groote, St. Louis, and Kwan-Ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Original application June 26, 1953, Serial No. 364,505, now Patent No. 2,771,429,:dated November v20, 1956. Divided and this application September 1 11, 1956, Serial No. 609,100

4 Claims. 01. zoo-45.1

The present invention is a continuation-in-part of our copending application, Serial No. 338,577, filed February 24, 1953, now US. Patent 2,771,439, and a division of our copending application Serial No. 364,505, filed June 26, 1953, now US. Patent 2,771,429. I u "Our invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. Our invention is also concerned with the application of such chemical products or compounds in various other arts and industries 1 as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

The present invention is concerned with a three-step manufacturing process involving (1) condensing certain phenol aldehyde resins, hereinafter described in'detail, with certain cyclic amidines, hereinafter described in detail, and formaldehyde; (2) oxyalkylation of the condensation product with certain phenolic polyepoxides hereinafter described in detail; and (3) oxyaikylation of the previously oxyalkylated resin condensate with certain monoepoxides, also hereinafter described in detail.

For a number of reasons it is usually most desirable to use the diepoxide type of polyepoxide. In preparing diepoxides or the low molal polymers one usually obtains cogeneric materials which may include monoepoxides. However, the cog'eneric mixture is invariably characterized by the fact that there is on the average, based on the molecular weight, of course, more than one epoxide group per molecule.

A more limited aspect of the present invention is represented by the use of products wherein the polyepoxide is represented by 1) compounds of the following formula and (2) cogenerically associated compounds formed in the preparation of (1) preceding, with the proviso that it consists principally of the monomer as distinguished from other cogeners.

Notwithstanding the fact that subsequent data will be 65.

presented in considerable detail, yet the description becomes somewhat involved and certain facts should be, kept in mind. The epoxides, and particularly the diepoxides may have no connecting bridge between the phenolic nuclei as in the case of a diphenyl .derivative or 70 ,m'ay have a variety of connecting bridges, i.e., divalent linking radicals. Our preference is that either diphenyl 2,888,431 Patented May 26, 1959 2 compounds be employed or else compounds whereithe di valent link is obtained by the removal of a carbonyl oxygen atom as derived from a ketone or aldehyde. If it were not for the expense involved in preparing 5 and purifying the monomer we would prefer itlto any other form, i.e., in preference to-the polymer or mixture of polymer and monomer. I

, Stated another way, we would prefer to use materials of the kind described, for example, in US. Patent No. 2,530,353, dated November 14,1950. Said patent describes compounds having the general. formula wherein R is an aliphatic hydrocarbon bridge, each n independently has one of the values 0 and ,1, and X is an alkyl radical containing from 1 m4 carbon atoms; I

The compounds having two oxirane rings and employed for combination with'the reactive amine-modified phenolaldehyde resin condensates as herein described are characterized by the following formula and cogenerically associated compounds formed in their preparation:

in which R represents a divalent radical selected firomthe classe of ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residues obtained vby the elimination of the aldehydic oxygen atoin, the

divalent radical r the divalent I i 7 Q a radical, the divalentsulfone radical, and the divalent monosulfide radical -S-, the divalent radical I CH SCH and the divalent disulfide radical+S-S'-; and'R O is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atomfro m'the phenol i III I! in which R, R", and R represent hydrogenand carbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; n repreferentiate from a reactant which, is not soluble and be not onlyinsoluble but also infusible I-iurtherrriore,

solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with the amine resin condensate. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as, for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglyco1.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i.e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxy butane (l,2-3,4 diepoxybutane) Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenol-aldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei and there may be present reactive hydrogen atoms attached to a nitrogen atom, or an oxygen atom, depending on the presence of a hyd-roxylated group or secondary amino group.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i.e., the compound having 2 oxirane rings and an amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of 2 moles of the amine condensate to one mole of the oxyalkylating agent gives a product which may 'be indicated as follows:

of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone.

A mere examination of the nature of the products before and after treatment with the polyepoxide reveals that the polyepoxide by and large introduces increased hydrophobe character or, inversely causes a decrease in hydrophile character. However, the solubility characteristics of the final product, i.e., the product obtained by oxyalkylation of a monoepoxide, may vary all over the map. This is perfectly understandable because ethylene oxide, glycide, and to a lesser extent methyl glycide, introduce predominantly hydrophile character, while propylene oxide and more especially buty-lene oxide, introduce primarily hydrophobe character. A mixture of the various oxides will produce a balancing in solubility characteristics or in the hydrophile-hydrophobe character so as to be about the same as prior to oxyalkylation with the monoepoxide.

The oxyalkylated polyepoxide treated condensates obtained in the manner described are, in turn, oxyalkylationsusceptible and valuable derivatives can be obtained by further reaction with other alkylene oxides, for instance, styrene (phenyl ethylene oxide), cyclohexyl ethylene oxide, ethylene imine, propylene imine, acrylonitrile, etc.

Similarly, the oxyalkylated polyepoxide-derived com pounds can be reacted with a product having both a nitrogen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See US. Patent No. 2,520,093, dated August 22, 1950 to Gross.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprises fine droplets of naturally occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing in which the various characters have their previous significance and the characterization condensate is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such intermediate product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form which is the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersi'ble in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their weight of 5% gluconic acid at ordinary tem- "perature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, 80 parts of xylene and '20 parts of methanol, or 70 parts of xylene and 30 parts for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i.e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufficiently hydrophile character to at least meet the test set forth in US. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a waterinsoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent 's'oluble'liquids or low-melting solids.

'are more than two epoxide groups per molecule. ,for practical purposes what is said hereinafter is largely D such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto ap- (pended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided into ten parts with Part 3, in turn, being divided into three subdivisions: Part 1 is concerned with our preference in regard to the 'polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of -diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation 'of monomeric diepoxides, including Table I;

Part 3, Subdivision B, is concerned with thepreparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 5 is concerned with appropriate basic cyclic amidines which may be employed in the preparation of the herein-described amine-modified resins;

Part 6 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to reaction with polyepoxides;

Part 7 is concerned with the reactions involving the two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves nothing more than a reaction between 2 moles of a previously prepared amine-modified phenol-aldehyde resin condensate as described, and one mole of a polyepoxide so as to yield a new and larger resin molecule, or comparable product;

Part 8 is concerned with the use of a monoepoxide in oxyalkylating the products described in Part 7, preceding, i.e., those derived by means of reaction between a polyepoxide and an amine-modified phenol-aldehyde resin as described;

Part 9 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds of reaction products; and

Part 10 is concerned with uses for the products herein described, either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solvent- Indeed, they tend to form thermosetting resins or insoluble materials.v Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoexpo'xides and as free as possible from polyepoxides in which tllilere T us,

limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxidesusually resultsin the formation of a c 0 generic mixture as explained subsequently. 1 Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually ex:- pensive. If monomers were available commercially ata low cost, or if they could be prepared without added ex pense for separation, our preference'would be to use the monomer. Certain monomers have been prepared and described in the literature and will be ,referred, to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomerfhas' over other low molal polymers from a cost standpoint; thus, we have found that. one mightjas well attempt to prepare a monomer and fully recognize that theremay be present, and probably invariably are present ptli'er low molal polymers in comparatively small am'ount's'l" Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means in stances where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyzl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples. f

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our 'preference is to produce them by means ofthe epichloro'h'ydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyldirnethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides in which there, is no bridging radical or'the. bridging radical is de rived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived 7 from the other groups illustrated for the reason that nothing more than mere substitution of one compound for the other would be required. Thus, what is said hereinafter, although directed to one class or a few classes,

8 PART 3 Subdivision A The preparations of the diepoxy derivatives of the diapplies with equal force and effect to the other classes phenols, which are sometimes referred to as diglycidyl of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfurcontaining compound can react with epichlorohydrin there may be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration.

ethers, have been described in a number of patents. For convenience, reference will be made to two only, to wit, aforementioned U.S. Patent 2,506,486, and aforementioned U.S. Patent No. 2,530,353.

Purely by way of illustration, the following diepoxides, or diglycidyl others as they are sometimes termed, are included for purpose of illustration. These particular compounds are described in the two patents just mentioned.

TABLEI Ex- Patent ample Diphenol Dlglycldyl ether refernumber enee OHQ(O6H4OH)2 Di(epoxypropoxyphenyl)methane 2,506,486 CH3CH(OH4O )1 Di(epowpropoxyphenybmethylmethane. 6, (CH3)2O(G@H4OH)2, Di(epoxypropoxyphenyl)dimethylmethane 2, 506,486 CgH C(OHz)(GuH4OH) Di(epoxypropoxyphenyl)ethylmethylmethana 2,506, 6 (C2H5)2G(C 1H4O )4". Di(epoxypropoxyphenyl)diethylmethane 2,506,486 OH3C(G3H )(C6H4OH);. Di(epoxypropo\yphenyl)rnethylpropylmethana 2,506,486 CH3C(C.-,H5)(GH4OH)2 Dl(eporypropoxyphenyl)methylphenvlmetnane. 2,506,486 C H C (C611 (OBI-L0H), D1(epotypropoxyphenyl)ethylphenylmethanm 2, 506, 486 G H O(C,H )(C H4OH) Di(epoxypropoxyphenyl)propylphenylmethane 2,506,486 G4H9C(CBI{5)(G5H4OH)2 Dl(epoxypropoxypheuyl)butylphenylmethane.. 2,506,486 (OH3C5I{4)CH(C$H4OH)1 .2 Di(epoxypropoxyphenyl)tolylmethane 2,506,486 (CH;O@H4)G(OH3)(C@H4OH)L Di(epoxypropoxyphenyl)tolylmethylmethane. 2,506,486 Dihydroxy diphenyl 4,4-bls(2,3-epoxypropoxy)dlphen 2,530,353 (CH3)C(C4H;,C@H3OH) 2,2-bis(4-(2,3-epoxypropoxy)2-tertiarybutyl phenyl)pr0pane 2, 530, 353

PART 2 SMbdlVlSlOn B The polyepoxides and particularly the diepoxides can be derived by more than one method as, for example, the use of epichlorohydrin or glycerol dichlorohydrin. A number of problems are involved in attempting to produce these materials free from cogeneric materials of related composition. For a discussion of these difficul- As to the preparation of low-molal polymeric epoxides or mixtures reference is made to numerous patents and particularly the aforementioned U.S. Patents Nos. 2,575,- 558 and 2,582,985.

In light of aforementioned U.S. Patent No. 2,575,558, the following examples can be specified by reference to ties, reference is made to U.S. Patent No. 2,819,212, the formula therein provided one still bears in mind it is beginning at column 7, line 21.

H: H H:

in essence an over-simplification.

TABLE II (in which the characters have their previous significance) Example -R O from HR OH -R n 11 Remarks number B1 Hydroxy benzene OH; 1 0, 1, 2 Phenol known as bis-phenol A. Low l polymeric mixture about 86 or more O where n=0, remainder largely Where I 'n=1, some where 1::2. CH:

B2 .do CH; 1 0, 1, 2 Phenol known as bis-phenol 13. See note regarding B1 above. I r CH:

B3-- Orthobutylphenol CH; 1 0, 1, 2 Even though 12 is preferably 0, yet the I usual reaction product might well con- -O tain materials where n is 1, or to a l lesser degree 2. CH3

B4 Orthoamylphenol (EH: 1 0, 1,2 Do.

111 Subdivision C The prior examples have been limited largely to those in which there is no divalent linking radical, as in the. case of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employedin converting diphenyl into a diglycidyl ether regardless of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepox ide, reactant. I

As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and may be illustrated by aphenol of the following composition:

3 I CH3 CH wherein R is a substituent selected fom the class con-. sisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbon atoms. See U.S. Patent No. 2,515,907.

H(OC;H )9O O(C,H,0 .H

l u u I-U a n C Hu Ca ii in which the -C H groups are secondary amyl groups. See U.S. Patent No. 2,504,064.

l u ia IK -1a HO OH See U.S. Patent No. 2,285,563.

H CH CH CHrJJ-CH; CH

CH; JH-CH;

G 3 CH See U.S. Patent No".- 2,503,196.

wherein R is a member of the group consisting of alkyl, and alkoxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U.S. Patent No. 2,526,545.

wherein R is a substituent selected from the class consistiug of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of 'alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See U.S. Patent No. 2,515,906.

CH=CH OH 0:011 011 As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly compounds such as H H O O Alkyl Alkyl Alkyl Alkyl v di(dialkyl cresol) sulfides which include the monosulfides,

the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention:

OH CH CH OH -in which R; and R are alkyl groups, the sum of whose PART 4 It is-well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula above formula in represents a small whole number varying from l'to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vecuum as described in the literature.

A limitedsub-genus is in the instance of low molecularweight polymers where the total number of phenol nuclei varies from 3 to 6, i.e., it varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms, such as a butyl, arnyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean 'it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from tri-functional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance parapheuylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzone, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U.S. Patent No. 2,499,365, dated March 7, 1950; to De Groote and Keiser.

The resins'herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene; This presents no problem insofar that all that is 'requiredis to make a solubility test on commercially available resins, or else prepare resins which are xylene orbenzene-soluble as described in aforementioned U.S. Patent'No. 2,499,365, or in U.S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resins having an average molecular weight corresponding to at least 3 and not over-6 phenolic nuclei per resin molecule. These resins aredifunctional only in regard to methylol-forming reactivity, are derived by reaction between a difunctional r'nonohydric phenol and an aldehyde having not over 8 carbon atoms and .reactive toward said phenol, and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in 'WhichR is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

If'one selected a resin of the kind just described previously and reactedapproximately one mole of the resin with, two moles of formaldehyde and two moles of a cyclic amidine as specified, following the same idealized tained appears to be described best in terms of'the method '1 4 over-simplification previously referred to, the i'e'sultafnt product might be illustrated thus: 1

. The cyclic amidine may bei designated thus:

' bine with the resin molecule, or even to a .very slight extent, if at all, 2 resin units may combine without anv amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes onecan use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

v 011 OH "I OH I URI/I 1 1110 v v A R R .L R

in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obof manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known;v See previ-* ously mentioned U.S.- Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst amount may be as small as a 200th of a percent and as having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst,

such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The

much as a few l0ths-of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used.- practically However, ,the most desirable procedure in every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i.e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE III M01. wt. of resin molecule on n+2) RI]! derived 1:

from

Example number Position of R Para Tertiary butyl Secondary butyL Tertiary amyl Mixed secondary and tertiary amyl.

Dodecyl Tertiary butyl Tertiary amyl Nonyl Tertiary butyl Tertiary amyl Nonyl Tertiary butyl.

onyl Tertiary butyl Tertiary amyl PART 5 The expression cyclic amidines is employed in its usual sense to indicate ring compounds in which there are present either 5 members or 6 members, and having 2 nitrogen atoms separated by a single carbon atom supplemented by either two additional carbon atoms or three additional carbon atoms completing the ring. All the carbon atoms may be substituted. The nitrogen atom of the ring involving two monovalent linkages may be substituted. Needless to say, these compounds include members in which the substitutents also may have one or more nitrogen atoms, either in the form of amine nitrogen atoms or in the form of acylated nitrogen atoms.

These cyclic amidines are sometimes characterized as being substituted imidazolines and tetrahydropyn'midines in which the two-position carbon of the ring is generally bonded to a hydrocarbon radical or comparable radical derived from an acid, such as a low molal fatty acid, a high molal fatty acid, or comparable acids such as polycarboxy acids.

Cyclic amidines obtained from oxidized wax acids are described in detail in vco-pending Blair application, Serial No. 274,075, filed February 28, 1952. Instead of being derived from oxidized wax acids, the cyclic compounds herein employed may be obtained from any acid from acetic acid upward, and may be obtained from acids, such as benzoic, or acids in which there is a reoccurring" ether linkage in the acyl radical. In essence then, with this difierence said aforementioned co-pending Blair application, Serial No. 274,075, describes compounds of the following structure:

where R is a member of the class consisting of hydrocarbon radicals having up to approximately 30 carbon atoms and includes hydroxylated hydrocarbon radicals and also hydrocarbon radicals in which the carbon atom chain is interrupted by oxygen; n is the numeral 2 to 3, D is a member of the class consisting of hydrogen and organic radicals containing less than 25 carbon atoms, composed of the elements from the group consisting of C, N, O and H, and B is a member of the group consisting of hydrogen and hydrocarbon radicals containing less than 7 carbon atoms, with the proviso that at least three occurrences of B are hydrogen.

The preparation of an imidazoline substituted in the two-position by lower aliphatic hydrocarbon radicals is, described in the literature and is readily carried out by reaction between a monocarboxylic acid or ester or amide and a diamine or polyamine, containing at least one primary amino group, and at least one secondary amino group or a second primary amino group separated from the first primary amino group by two carbon atoms.

Examples of suitable polyamines which can be employed as reactants to form basic nitrogen-containing compounds of the present invention include polyalkylene polyamines such as ethylene-diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and higher polyethylene polyamines, and also including 1,2-diaminopropane, N-ethylethylenediamine, N,N-dibutyldiethylenetriarnine, 1,2-diaminobutane, hydroxyethylethylenediamine, 1,2-propylenetriamine, and the like.

Equally suitable for use in preparing compounds of our invention and for the preparation of tetrahydropyrimidines substituted in the 2-position are the polyamines containing at least one primary amino group and at least one secondary amino group, or another primary amino group separated from the first primary amino group by three carbon atoms. This reaction is generally carried out by heating the reactants to a temperature of 230 C. or higher, usually within the range of 250 C. to 300 C., at which temperatures water is evolved and ring closure is efi'ected.

Examples of amines suitable for this synthesis include 1,3-propylenediamine, trimethylenediamine, 1,3+diaminobutane, 2,4-diaminopentane, N-ethyl-trimethylenediamine, N-aminoethyl-trimethylenediamine; aminopropyl stearylamine, tripropylenetetramine, tetrapropylenepentamine,

high boiling polyamines prepared by the condensation of 1,3-propylene dichloride with ammonia, and similar diamines or polyamines in which there occurs at least one primary amino group separated from another primary or secondary amino group by three carbon atoms.

Similarly, the same class of materials are included as initial reactants in co-pending Smith application, Serial No. 281,645, filed April 10, 1952. The present invention is concerned with a condensation reaction, in which one class of reactants are substituted ring compounds in which R is a divalent alkylene radical of the class of -cH,oH,- 'CHiCHjCHF H -C-CHr and in which D' represents a divalent, non-amino, organic radical containing less than 25 carbon atoms, composed of elements including C, H, O, and r; Y represents a divalent, organic radical containing less than 25 carbon atoms, composed of elements including C, H, O, and N, and containing at least one amino group, and R in cludes hydrogen, aliphatic hydrocarbon radicals, hydroxylated aliphatic hydrocarbon radicals, cycloaliphatic hydrocarbon radicals, and hydroxylated cycloaliphatic hydrocarbon radicals; R" includes hydrogen, aliphatic radicals and cycloaliphatic radicals.

As to the six-membered ring compounds generally referred to as substituted pyrimidines, and more particularly as substituted tetra-hydropyrimidines, see US. Patent No. 2,534,828, dated December 19, 1950, to Mitchell et al. With the modification as far as the instant application goes, the hydrocarbon group R may have the same variation as when it is part of the five-membered ring previously referred to and is not limited to an alkyl group having at least 10 carbon atoms as in the instance of the aforementioned US. Patent No. 2,534,828. t

For the purpose of the present invention there is selected from the broad case of compounds previously described such members as meet the following limitations: (a) Have present at least one basic secondary amino radical; and (b) be free from primary amino groups and especially basic primary amino groups. Such compounds may have two ring membered radicals present instead of one ring-membered radical and may or may not have present a tertiary amine radical or a hydroxyl radical, such as a hydroxy alkyl radical. A large number of compounds have been described in the literature meeting the above specifications, of which quite a few appear'in the aforementioned issued US. Patents. Examples selected from the patents include the following:

N-CH:

CuHn- (1) N- H; lit

2-undecy1imidazoline /NCH: cflnmo 2) 2-heptadecylimidazo11ne N-CH;

CnHaJJ 2-oleylimidazoltne N-CH,

C|H|.O

C|H|.NH.C10H11 l-N-decylaminoethyl,2-ethyllmldezol1ne N-CH:

CzH4.NH.CzH4.NH-CuHu 2'-methy1,l-hexsdecylaminoethylaminoethylimidazoline N Hg CzHpIILCzHpNHO C .CH|

012B 1- (N-dode cyl) -acetamidoethylaminoethylimidazoline N-CH-OH:

CHEN-C (10) H-CH: 2-heptadecy1,4,5-dimethyllmldazoltne N--CH: H-C

oHn-NHflnHax 1-dodecylaminohexylimidazoline CQH12.NH.CQH4.O 013E l-stearoyloxyethylaminohexylimldazoline %N-Cgn CnHaa-C CH:

2-heptadecy1,l-methylaminoethyltetrahydropyrimidlne N-CH-CH:

CuHn-C CH:

N-CH:

sEhNH 0,34

4-mathyl,2-dodecy1,1-methy]aminoethylaminoethyltetra- J hydropyrimidine As has been pointed out previously, the reactants herein employed may have two substituted imidazoline rings or two substituted tetrahydropyn'midine rings. Such compounds are illustrated by the following formula:

Such compounds can be derived,'of course, from triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and higher homologuesr The substituents may vary depending on the source of the hydrocarbon radical;

19 such as the lower fatty acids and higher fatty acids, a resin acid, naphthenic acid, or thelike. The group in troduced may or may not contain a hydroxyl radical as in the case of hydroxyacetic acid, acetic acid, ricinoleic acid, oleic acid, etc.

One advantage of a two-ring compound resides in the fact that primary amino groups which constitute the terminal radicals of the parent polyamine, whether a polyethylene amine or polypropylene amine, are converted so as to eliminate the presence of such primary amino radicals. Thus, the two-membered ring compound meets the previous specification in regard to the nitrogencontaining radicals.

Another procedure to form a two-membered ring compound is to use a dibasic acid. Suitable compounds are described, for example, in aforementioned US. Patent No. 2,194,419, dated March 19, 1940, to Chwala.

As to compounds having a tertiary amine radical, it is obvious that one can employ derivatives of polyarnines in which the terminal groups are unsymmetrically alkylated. Initial polyamines of this type are illustrated by the following formula:

in which R represents a small alkyl radical such as methyl, ethyl, propyl, etc., and n represents a small whole number greater than unity such as 2, 3 or 4. Substituted imidazolines can only be formed from that part of the polyamine which has a primary amino group present. There is no objection to the presence of a tertiary amino radical as previously pointed out. Such derivatives, provided there is more than one secondary amino radical present in the ring compound, may be reacted with an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., so as to convert one or more amino nitrogen radicals into the corresponding hydroxy alkyl radical, provided, however, that there is still a residue secondary amine group. For instance, in the preceding formula if n represents 4 it means the ring compound would have two secondary nitrogen radicals and could be treated with a single mole of an alkylene oxide and still provide a satisfactory reactant for the herein described condensation reaction.

Ring compounds, such as substituted imidazolines, may be reacted with a substantial amount of akylene oxide as noted'in the preceding paragraph and then a secondary amino group introduced by two steps; first, reaction with an ethylene imine, and second, reaction with another mole of the oxide, or with an alkylating agent such as dimethyl sulfate, benzyl chloride, a low molal ester of a sulfonic acid, an alkyl bromide, etc.

As to oxyalkylated imidazolines and a variety of suitable high molecular weight carboxy acids which may be the source of a substituent radical, see US. Patent No. 2,468,180, dated April 26, 1949, to De Groote and Keiser.

Other suitable means may be employed to eliminate a terminal primary amino radical. If there is additionally a basic secondary amino radical present then the primary amino radical can be subjected to acylation notwithstanding the fact that the surviving amino group has no significant basicity. As a rule acylation takes place at the terminal primary amino group rather than at the secondary amino group, thus one can employ a compound such as N-CH:

N C E:

C1H4.NH.C2H4.NH1 2-heptadeey1,1-diethy1enediaminoirnidazoline and subject it to acylation so as to obtain, for example, acetylated 2 heptadecyl,1-diethylenediarninoimidazoline of the following structure:

Similarly, a compound having no basic secondary amino radical but a basic primary amino radical can be reacted with a mole of an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., to yield a perfectly satisfactory reactant for the herein described condensation procedure. This can be illustrated in the following manner by a compound such as NCH: Cl'lHtlr-Q N-CE1 C2H4.NH; 2-heptadecy1,l-aminoethylimidazoline which can be reacted with a single mole of ethylene oxide, for example, to produce the hydroxy ethyl derivative of 2-heptadecyl,l-amino-ethylimidazoline, which can be illustrated by the following formula:

N-OH,

C IHLN Other reactants may be employed in connection with an initial reactant of the kind described above, to wit, 2-

heptadecyl,1-amino-ethylimidazoline; for instance, reaction with an alkylene imine such as ethylene imine, propylene imine, etc. If reacted with ethylene imine the net result is to convert a primary amino radical into a secondary amino radical and also introduces a new primary amino group. If ethylene imine is employed, the net result is simply to convert 2-heptadecyl,1-aminoethylimidazoline into 2-heptadecyl,l-diethylene-diaminoimidazoline. However, if propylene imine is used the net result is a compound which can be considered as being derived hypothetically from a mixed polyalkylene amine, i.e., one having both ethylene groups and a propylene group between nitrogen atoms.

A more satisfactory reactant is to employ one obtained by the reaction of epichlorohydrin on a secondary alkyl amine, such as the following compound:

If a mole of Z-heptadecyl,l-aminoethylimidazoline is re- 21' acted with a mole of the compound just described, to wit,

H H H l T7 CzH4 O The resultant compound has a basic secondary amino group and a basic tertiary amino group. See U.S. Patent No. 2,520,093 dated August 22, 1950, to Gross.

For purpose of convenience, what has been said by direct reference is largely by way of illustration in which there is present a sizable hydrophobe group, for instance, heptadecyl groups, pentadecyl groups, octyl groups, nonyl groups, etc. etc.

As has been pointed out, one can obtain all these comparable derivatives from low rnolal acids, such as acetic, propionic, butyric, caleric, etc. Similarly, one can employ hydroxy acids such as glycolic acids, lactic acid, etc. Over and above this, one may employ acids which introduce a very distinct hydrophobe elfect as, for example, acids prepared by the oxyethylation of a low molal alcohol, such as methyl, ethyl, propyl, or the like, to produce compounds of the formula R OCH CH OH in which R is a low molal group, such as methyl, ethyl or propyl, and n is a whole number varying from one up to 15 or 20. Such compounds can be converted into the alkoxide and then reacted with an ester of chloracetic followed by saponification so as to yield compounds of the type R(OCH CH ),,OCH COOH in which n has its prior significance. Another procedure is to convert the compound into a halide ether such as in in which n has its prior significance, and then react such halide ether with sodium cyanide so as to give the corresponding nitrile R(OCH CH ),,CN, which can be converted into the corresponding acid, of the following composition R(OCH CH ),,COOH. Such acids can also be used to produce acyl derivatives of the kind previously described in which acetic acid is used as an acylating agent.

What has been said above is intended to emphasize the fact that the nitrogen compounds herein employed can vary from those which are strongly hydrophobe in character and have a minimum hydrophobe property.

Examples of decreased hydrophobe character are exemplified by 2-methylimidazoline, 2-propylimidazoline, and

2-butylimidazoline, of the following structures:

N-CH:

CgH4.C (17) N-CH:

C(HO-O (19) N-CH: 1';

PART 6 Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557, in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U.S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively nonvolatile solvent such as dioxane or the diethylether of ethyleneglycol. One canalso use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, para-formaldehyde can be used but it is more difiicult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there. is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost s earer water-white in color or at least a red-amber, or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and on the amine selected the condensation product or reaction mass on a solvent-free basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. in fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 150 C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i.e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (12) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation?; and the third factor is this, (0) is an effort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove the water-soluble unreacted fornialdehyde, if any, or a water-wash to remove any unreacted water-insoluble polyamine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found xylene the most satisfactory solvent.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general wa bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling 24 or helps distribution of the incoming formaldehyde; This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more in-terfacial the area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U.S. latent 2,499,368. After the resin is in complete solution the polyarnine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueousformaldehyde solution. If so, the resin then will dis solve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a two-phase.

system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. Thetend to decrease any formaldehyde loss or make it easier" to control unreacted formaldehyde loss.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or

at the most, up to 10-24 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phaseseparating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about C., and generally slightly above 100 C., and below C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned US Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of nitrogen compound, and, again, have not found any particular advantage in so doing:

Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the endproduct showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 1a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3% phenolic nuclei, as the value for n which excludes the 2 external nuclei, i.e., the resin was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color. 7

882 grams of the resin identified as 1a, preceding, were powdered and mixed with a somewhat lesser amount of xylene, i.e., 600 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 35' C. and 612 grams of 2-oleylimidazoline, preuntil the temperature reached approximately 148 C;

The mass was kept at this higher temperature for 3 or 4 hours. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene. The residual material was dark red in color and had the consistency of a thick sticky fluid or tacky resin. The overall reaction time was approximately 30 hours. In other examples it varied from as little as 24 hours up to approximately 38 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6 hours. Note that in Table IV following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150" C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure'is illustrated by 24 examples in Table IV.

TABLE IV Amt. of Strength of Reac- Reac Max. Ex. Resin Amt Amine used amine, formaldehyde Solvent used tlon tion distill. No. used grs. grams soln. and amt. and amt. temp., time temp.,

0. (hrs) C.

612 37%, 162 g..- Xylene, 600 g. 20-25 30 148 37 81 Xylene, 450 g 21-23 24 145 Xylene, 600 g 20-22 28 150 Xylene, 400 g 22-24 28 148 Xylene, 450 g 21-23 30 148 Xylene, 600 g 21-25 26 146 Xylene, 400 g. 23-28 26 147 Xylene, 450 55.... 22-26 26 146 Xylene, 600 g 21-25 38 150 ylene, 450 g 20-24 36 149 Xylene, 500 g 21-22 24 142 Xylene, 650 g--- 20-21 26 145 ylene, 425 g. 22-28 28 146 Xylene, 450 g 23-30 27 150 Xylene, 550 g 20-24 29 147 Xylene, 440 g. 20-21 30 148 ylene, 480 g- 21-26 32 146 Xylene, 600 g. 21-23 26. 147 Xylene, 500 g 21-32 29 150 Xylene, 500 g. 21-30 32 150 Xylene, 550 an... 21-23 37 150 Xylene, 4 g-. 20-22 30 150 Xylene, 600 g. 20-26 36 149 Xylene, 400 g 20-24 32 152 viously shown in a structural formula as ring compound (3), were added. The mixture was stirred vigorously and formaldehyde added slowly. In this particular case the formaldehyde used was a 37% solution and 162 grams were added in approximately 3 hours. The mixture was stirred vigorously and kept within a range of approximately 40 to 44 C., for about 16 /2 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear in approximately three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all the water of solution and reaction. After PART 7 The products obtained as herein described by reactions involving amine condensation and diglycidyl ethers or the equivalent are valuable for use as such. This is pointed out in detail elsewhere. -However, in many instances the derivatives obtained by oxyalkylation are even more valuable and from such standpoint the herein described products may be considered as valuable intermediates. Subsequent oxyalkylation involves the use of ethylene oxide, propylene oxide, butylene oxide, glycide, etc. Such oxyalkylating agents are monoepoxides as diiferentiated from polyepoxides.

the water was eliminated part of the xylene was removed f It becomes apparent that if the product obtained is to 27 be treated subsequently with a monoepoxide' which may require a pressure vessel as in the case of ethylene oxide, it is convenient to use the same reaction vessel in both resin 3a was obtained from tertiary amylphenol andformaldehyde. Condensate 2b employed as reactants resin 3a and amine 3, referred to in Table IV preceding, and more instances. In other words, the 2 moles of the aminespecifically the compound Z-oleylimidazoline. The modified phenol-aldehyde resin condensate would be re- 5 amount of resin employed was 480 grams, the amount of acted with a polyepoxide and then subsequently with a Z-oleylimidazoline employed was 306 grams, the amount monoepoxide. In any event, if desired the polyepoxide of 37% formaldehyde employed was 81 grams, and the reaction can be conducted in an ordinary reaction vessel, amount of solvent employed was 450 grams. All this has such as the usual glass laboratory equipment. This is been described previously.

particularly true of the kind used for resin manufacture as The solution of the condensate in xylene was adjusted described in a number of patents, as for example, US to a 50% solution. In this particular instance, and in Patent No. 2,499,365. practically all the others which appear in a subsequent Cognizance should be taken of one particular feature table, the examples are characterized by the fact that no in connection with the reaction involving the polyepoxide alkaline catalyst was added. The reason is, of course, and that is this; the aminemodified phenol-aldehyde resin that the condensate as such is strongly basic. If-desired, condensate is invariably basic and thus one need not add a small amount of alkaline catalyst could be added, such the usual catalysts which are used to promote such re as finely powdered caustic soda, sodium methylate, etc. actions. Generally speaking, the reaction will proceed if such alkaline catalyst is added it may speed up the reat a satisfactory rate under suitable conditions without action but it also may cause an undesirable reaction, such any catalyst at all. as the polymerization of the diepoxide.

Employing polyepoxides in combination with a non- In any event, 160 grams of the condensate dissolved basic reactant the usual catalysts include alkaline matein approximately an equal weight of xylene were stirred rials such as caustic soda, caustic potash, sodium methyland heated to slightly above the boiling point of water. ate, etc. Other catalysts may be acidic in nature and are 17 grams of the diepoxide previously identified as 3A of the kind characterized by iron and tin chloride. FuI- 535 and dissolved in an equal weight of xylene were added thermore, insoluble catalysts such as clays or specially predropwise. The initial addition of the xylene solution carpared mineral catalysts have been used. If for any rearied the temperature to slightly above the boiling point of son the reaction did not proceed rapidly enough with the water. The remainder of the diepoxide was added durdiglycidyl ether or other analogous reactant, then a smml ing approximately a 50 minute period. During this peamoum 0f firmly divided Caustic soda of Sodium y 3O riod of time the temperature rose to about 122 C. The ate could be employed as a catalyst. Th m unt g ntemperature was allowed to rise slightly and the product erally employed would be 1% or 2%. refluxed at about 130 C. using a phase-separating trap.

It gOeS Without Saying that thfi action can take Place A small amount of xylene was removed by means of the in an inert solvent, i.e., one that is not oxyalkylation-susphase-separating trap so the temperature gradually rose ceptible. Generally speaking, this is most conveniently to 156 C. and the product was refluxed at this temperaan aromatic solvent such as Xylene a higher boiling ture for about 6 hours. After this period of time the C081 tar SOIVEIII, @156 a Similar high boiling at xylene which had been removed during the reflux period solvent obtained from petrol u One can 1 an was returned to the mixture. A small amount of material oxygenated solvent such as th di l/ 0f ethylene was withdrawn and the xylene evaporated on a hot plate glycol, of the diethylether 0f P py y of similar 40 in order to examine the physical properties. The maethers, either alone or in combination with a hydrocarbon te i l was a d k d Viscgus emi- 1id, It a i ol bl solvent. The selection of th Solvent p n in P 011 in water, and it was insoluble in 5% gluconic acid; it was the subsequent use of the derivatives or reaction prodl bl i ylene d particularly i a i t f 80% ucts. If the reaction products are to be rendered solventylene d 20% h l, H if h i l 128 and. it is 1166688313 that the SOlV6l1t b readily I8- was dissolved in an oxygenated solvent and then shaken moved for eXZImPIE, y the use of Vacuum distillation, with 5% gluconic acid it showed a definite tendency to thus xylene or an aromatic petroleum wil serve. if the disperse, suspend, or form a sol, and particularly in a pmdllC1 is going to 106 Subjected oXyalkylatiofl Subsexylene-methanol mixed solvent as previously described, q y, then the Solvent shvuld be one which is not Y- with or without the further addition of a little acetone. alkylation-susceptible. It is easy enough to select a suit Th procedure employed of course is simple in light of a l Solvent if Ifiqliiffid in y instance but, Everything what has been said previously and in effect is a procedure else being equal, the solvent chosen should be the most Similar to that employed in the use f .glycide or h 1 economlcal glycide as oxyalkylating agents. See, for example, Part 1 Example 16 Of Us. Patent No. 2,602,062 dated July 1, 1952, to

The product was obtained by reaction between the di- De Groote. epoxide previously designated as diepoxide 3A, and eon- Vanous examples obtained in substantially the same densate 2b. Condensate 2b was obtained from resin 30; manner are enumerated in the following tables:

TABLE v 0011- Dlep- Time Max. Ex. den- Amt., oxide Amt., Xylene, Molar 01' reactemp., Color and physical state No. sate grs. used grs. grs. ratio tion, 0.

used hrs.

160 3A 17 177 2:1 8 Dark solid mass. 3A 17 172 2:1 7 155 Do. 169 3A 17 186 2:1 8 158 D0. 177 3A 17 194 2:1 3 155 Do. 173 3a 17 190 211 s 160 Do. 211 at 17 228 2:1 8 152 Do. 3A 17 187 211 8 158 Do. 124 3A 17 141 2:1 6 160 Do. 125 3A 17 142 211 6 162 Do. 131 3A 17 148 2:1 6 158 D0.

Solubility in regard to all these compounds was substantially similar to that which was described in Example 10.

TABLE VI Oon- Dlep- Time Max. Ex. den- Amt., oxide Amt, Xylene, Molar of reactemp, Color and physical state N o. sate grs. used grs. grs. ratio tlon, 0.

used hrs.

160 B1 27. 188 2:1 8 155 Dark solid mass. 155 B1 27. 5 183 2:1 8 160 Do. 169 B1 27. 5 197 2:1 8 162 Do. 177 B1 27. 5 205 2:1 8 158 Do. 173 B1 27. 5 200 2:1 8 165 Do. 211 B1 27. 5 239 2:1 8 156 Do. 170 B1 27. 5 198 2:1 8 161 Do. 124 B1 27. 5 152 2:1 7 164 Do. 125 B1 27. 5 153 2:1 7 158 Do. 131 B1 27. 6 159 2:1 7 169 Do.

Solubility in regard to all these compounds was substantially similar to that which was described in Example 10.

TABLE VII Probable Probable Resin conmol. wt. of Amt. oi Amt. of number of Ex. N o. densate reaction product, solvent, hydroxyls used product grs. grs. per molecule TABLE VIII Probable Probable Resin con mol. wt. of Amt. of Amt. of number of Ex. No. densate reaction product, solvent, hydroxyls used product grs. grs. per molecule 1D 2b 3, 740 3, 740 1, 870 11 2D 5!; 3, 640 3, 625 1, 825 11 3D 75 3, 940 3, 950 1, 980 11 4D 85 4, 090 4, 100 2, 055 11 5D b 4,010 4,000 1,995 11 6D 1212 770 4, 775 2, 390 11 7D 13b 3, 940 3, 940 1, 970 15 BB 185 3, 040 3, 050 1, 530 11 9D 19!: 3, 040 3, 040 1, 520 12 1OD.- 20b 3, 170 3, 175 1, 590 12 like, such as the following:

H H H H H H H nococo-ooo-on H H may be employed to replace the diepoxides herein described. However, such derivatives are not included as part of the instant invention.

At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the [following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an'oxygenated solvent, such as the diethyl ether of ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance to instead of The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular weight by several percent.

Previously the condensate has been depicted in a simplified form which, for convenience, may be shown thus:

(Amine)CH (Resin)CH (Amine) Following such simplification the reaction product with a polyepoxide and particularly a diepoxide, would be indicated thus:

[(Amine) CHAResin) 0H, Am1ne)]\ [(Arnine) CH CResln) 0H, (Amine) 1 in which D.G.E. represents a diglycidyl other as specified. If the amine happened to have more than one reactive hydrogen, as in the case of a hydroxylated amine or polyamine, having a multiplicity of secondary amino groups it is obvious that other side reactions could take place as indicated by the following formulas:

[(Amine) CHz(Amine)] [D.G.E.]

[(Amine) 0H (Amlne)] Resin) CH,(Resin)] [D. G. E.]

[(Resin) GH (Resin)] 0Hi( m )l [D.G.E.]

[( Resin)] All the above indicates the complexity of the reaction product obtained after treating the amine-modified resin condensate with a polyepoxide and particularly diepoxide as herein described.

PART 8 The preparation of the compounds or products described in Part 7, preceding, involves an oxyalkylating agent, to wit, a polyepoxide and usually a diepoxide. The procedure described in the present part is a further oxyalkylation step but involves the use of a monoepoxide or the equivalent. The principal difference is only that while polyepoxides are invariably nonvolatile and can be reacted under a condenser, at least numerous monoepoxides and particularly ethylene oxide, propylene oxide, butylene oxide, etc., involve somewhat different operating conditions. Glyoide and methylglycide react under practically the same conditions as the polyepoxides. Actually, for purpose of convenience, it is involving the polyepoxide, in equipment such that subsequent reaction with monoepoxides may follow Without interruption. In the oxyalkylations carried out to produce compositions used in accordance with the present application, conventional equipment, i.e., a stainless steel autoclave suitably equpped, and conventional oxyalkylation conditions were use The amount of monoepoxides employed may be as high as 50 parts of monoepoxide for one part of the monoepoxide treated amine-modified phenol-aldehyde condensation product.

Example 1 E The polyepoxide-derived oxyalkylation-susceptible compound employed is the one previously designated and described as Example 1D. Polyepoxide-derived condensate ID was obtained, in turn, from condensate 2b and diepoxide B1. Reference to Table IV shows the composition of condensate 212. Table IV shows it was obtained from Resin a, Amine 3 and formaldehyde. Amine 3 is a 2-oleylimidazoline. Table III shows that Resin 5a was obtained from tertiary amylphenol (para-substituted) and formaldehyde.

For purpose of convenience, reference herein and in the tables to the oxyalkylation-sitsceptible compound will be abbreviated in the table heading as OSC; reference is to the solvent-free material since, for convenience, the amount of solvent is noted in a second column. Actually, part of the solvent may have been present and in practically every case was present in either the resinification process or the condensation process, or in treatment with a polyepoxide. In any event, the amount of solvent present at the time of treatment with a monoepoxide is indicated as a separate item. To be consistent, of course, the oxyalkylation-susceptible compound abbreviated as OSC is indicated on a solvent-free basis.

18.70 pounds of the polyepoxide-derived condensate were mixed with 18.70 pounds of solvent (xylene in this series) along with one pound of finely powdered caustic soda as a catalyst. This reaction mixture was treated with 9.35 pounds of ethylene oxide. At the end of the reaction period the molal ratio of oxide to initial compound was approximately 42.5, and the theoretical molecular weight was approximately 5,600.

Adjustment was made in the autoclave to operate at a temperature of 125 to 130 C., and at a pressure of to pounds per square inch.

The time regulator was set so as to inject the ethylene oxide in approximately one-half hour and then continued stirring for one-half hour longer simply as a precaution to insure complete reaction. The reaction went readily, and, as a matter of fact, the ethylene oxide could have been injected in probably 15 minutes instead of a halfhour and the subsequent time allowed to insure completion of reaction may have been entirely unnecessary. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to the excellent agitation and also to the comparatively high con centration of catalyst. The amount of ethylene oxide introduced, as previously noted, was 9.35 pounds.

A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned, and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data or subsequent data, or in data reported in tabular form in subsequent Tables IX, X and XI.

The size of the autoclave employed was 35 gallons. In innumerable oxyalkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example 2E This example simply illustrates further oxyalkylation of Example 1E, preceding. The oxyalkylation-susceptible compound, to wit, Example 1D, is the same one as was used in Example 1E, preceding, because it ismerely a continuation. In the subsequent tables, such as Table IX, the oxyalkylation-susceptible compound in the horizontal line concerned with Example 2E refers to oxyalkylation-susceptible compound, Example 1D. Actually, one could refer just as properly to Example 1E at this stage. It is immaterial which designation is used so long as it is understood and such practice is used consistently throughout the tables. In any event, the amount of ethylene oxide is the same as before, to wit, 9.35 pounds. This means the amount of oxide at the end was 18.70 pounds. It is meant that the ratio of oxide to oxyalkylation-susceptible compound (molar basis) at the end was to 1. The theoretical molecular weight was almost 7,500. There was no added solvent. In other words, it remained the same, that is, 18.70 pounds, and there was no added catalyst. The entire procedure was substantially the same as in Example 1E, preceding.

In all succeeding examples the time and pressure were the same as previously, to Wit, to C., and the pressure 10 to 15 pounds. The time element was onehalf hour, the same as before.

Example 3E The oxyethylation proceeded in the same manner as described in Examples 1E and 2E. There was no added solvent and no added catalyst. The oxide added was 9.35 pounds. The total oxide at the end of the oxyalkylation procedure was 28.05 pounds. The molal ratio of oxide to condensate was 127.5 to 1. The theoretical molecular weight was approximately 9,350. As previously noted, conditions in regard to temperature and pressure were the same as in Examples 1E and 2E. The time period was slightly longer, to wit, 45 minutes.

Example 4E The oxyethylation was continued and the amount of oxide added was the same as before, to wit, 9.35 pounds. The amount of oxide added at the end of the reaction was 37.4 pounds. There was no added solvent and no added catalyst. Conditions as far as temperature and pressure are concerned were the same as in previous examples. The time period was slightly longer, to wit, 1 /4 hours. The reaction at this point showed some tendency to slow up. The molal ratio of oxide to oxyalkylation-susceptible compound was about to 1 and the theoretical molecular weight was 11,220.

Example 5E The oxyalkylation was continued with the introduction of another 9.35 pounds of oxide. No added solvent was introduced, and likewise no added catalyst was introduced. The theoretical molecular weight at the end of the reaction was approximately 13,000. The molal ratio of oxide to oxyalkylation-susceptible compound was 212.5 to l. The time period was 1 /2 hours.

Example 6E The same procedure was followed as in the previous examples without addition of either more catalyst or more solvent. The amount of oxide added was the same as before, to wit, 9.35 pounds. The time required to complete the reaction was 1 /2 hours. At the end of the reaction the ratio of oxide to oxyalkylationsusceptible compound was approximately'255 to 1, and the theoretical molecular weight was about 15,000.

The same procedure as described in the previous examples was employed in connection with a number of the other condensations described previously. All these data have been presented in tabular form in Tables IX through XIV, inclusive.

In substantially every case a 35-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then 33 transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables IX, X and XI, it will be noted that compounds 1E through 18E were obtained by the use of ethylene oxide, whereas Examples 19E through 36E were obtained by the use of propylene oxide; and Examples 37E through 54E were obtained by the use of butylene, oxide.

Referring now to Table X specifically, it will be noted that the series of examples beginning with 1F were obtained, in turn, by use of both ethylene and propylene oxides, using ethylene first; in fact, using Example 2E as the oxyalkylation-susceptible compound in the first six examples. This applies to series 1F through 18F.

Similarly, series 19F through 36F involve the use of both propylene oxide and ethylene oxide in which the propylene oxide was used first, to wit, 19F was prepared from 24E, a compound which was initially derived by use of propylene oxide.

Similarly, Examples 37F through 54F involve the use of ethylene oxide and butylene oxide, the ethylene oxide being used first. Also, these two oxides were used in the series 55F through 72F, but in this latter instance the butylene oxide was used first and then the ethylene oxide.

Series 73F through 90F involve the use of propylene oxide and butylene oxide, butylene oxide being used first and propylene oxide being used next.

In series 1G through 186 the three oxides were used. It will be noted in Example 1G the initial compound was 77F; Example 77F, in turn, was obtained from a compound in which butylene oxide was used initially and then propylene oxide. Thus, the oxide added in the series 1G through 66 was by use of ethylene oxide as indicated in Table XI.

Referring to Table XI, in regard to Example 19G it will be noted again that the three oxides were used and 196 was obtained from 60F. Example 60F, in turn, was obtained by using butylene oxide first and then ethylene oxide. In Example 196 and subsequent examples, such as 206, 21G, etc., propylene oxide was added.

Tables XII, XIII and XIV give the data in regard to the oxyalkylation procedure as far as temperature and pressure are concerned and also give some data as to solubility of the oxyalkylated derivative in water, xylene and kerosene.

Referring to Table IX in greater detail, the data are as follows: The first column gives the example numbers, such as 1E, 2E, 3E, etc. etc.; the second column gives the oxyalkylation-susceptible compound employed which as previously noted in the series 1E through 6E, is Example 1D, although it would be just as proper to say that in the case of 2B the oxyalkylation-susceptible compound was 1E, and in the case of 3B the oxyalkylation-susceptible compound was 2E. Actually reference is to the parent derivative for the reason that the figure stands constant and probably leads to a more convenient presentation. Thus, the third column indicates the polyepoxide-derived condensate previously referred to in the text.

The fourth column shows the amount of ethylene oxide in the mixture prior to the particular oxyethylation step. In the case of Example 1E there is no oxide. used but it appears, of course, in 2E, 3E and 4E, etc.

The fifth column can be ignored for the reason that it is concerned with propylene oxide only, and the sixth column can be ignored for the reason that it is concerned with butylene oxide only.

The seventh column shows the catalyst which is invariably powdered caustic soda. The quantity used is indicated.

The eighth column shows the amount of solvent which is xylene unless otherwise stated.

The ninth column shows the amount of oxyalkylationsusceptible compound which in this series is the poly-' epoxide-derived condensate.

The tenth column shows the amount of ethylene oxide in at the end of the particular step.

Column eleven shows the same data for propylene oxide, and column twelve for butylene oxide. For obvious reasons these can be ignored in the series 1E through 18E.

Column thirteen shows the amount of the catalyst at the end of the oxyalkylation step, and column fourteen shows the amount of solvent at the end of the oxyalkylation step.

The fifteenth, sixteenth and seventeenth columns are concerned with molal ratio of the individual oxides to the oxyalkylation-susceptible compound. Data appears only in column fifteen for the reason, previously noted, that no butylene or propylene oxide were used in the present instance.

The theoretical molecular weight appears at the end of the table which is on the assumption, as previously noted, as to the probable molecular weight of the initial compound, and on the assumption that all oxide added during the period combined. This is susceptible to limitations that have been pointed out elsewhere, particularly in the patent literature.

Referring now to the second series of compounds in Table IX, to wit, Examples 19E through 36E, the situation is the same except that it is obvious the oxyalkylating agent used was propylene oxide and not'ethylene oxide. Thus, the fourth column becomes a blank and the tenth column becomes a blank and the fifteenth column becomes a blank, but column five, which previously was a blank in Table IX now carries data as to the amount of propylene oxide present at the beginning of the reaction.

Column eleven carries data as to the amount of propylene oxide present at the end of the reaction, and column sixteen carries data as to the ratio of propylene oxide to the oxyalkylation-susceptible compound. In all other instances the various headings have the same significance as previously.

Similarly, referring to Examples 37E through 54E in Table IX, columns four and five are blanks, columns ten and eleven are blanks, and columns fifteen and sixteen are blanks, but data appear in column six as to butylene oxide present before the particular oxyalkylation step. Column twelve gives the amount of butylene oxide present at the end of the step, and column seventeen gives the ratio of butylene oxide to oxyalkylation-susceptible compound.

Table X is in essence the data presented in exactly the same way except the two oxides appear, to wit, ethylene oxide and propylene oxide. This means that there are only three columns in which data does not appear, all three being concerned with the use of butylene oxide. Furthermore, it shows which oxide was used first by the very fact that reference to Example 1F, in turn, refers to 2E, and also shows that ethylene oxide was present at the very first stage. Furthermore, for ease of comparison and also to be consistent, the data under Molal Ratio in regard to ethylene oxide and propylene oxide goes back to the original diepoxide-derived condensate 1D. This is obvious, of course, because the figures 85.0 and 64.5 coincide with the figures for 2E derived from ID, as shown in Table IX.

In Table X the same situation is involved except, of course, propylene oxide is used first and this, again, is perfectly apparent. Three columns only are blank, to wit, the three referring to butylene oxide. The same situation applies in examples such as 37F and subsequent examples where the two oxides used are ethylene oxide and butylene oxide, and the table makes it plain that ethylene oxide was used first. Inversely, Example 55F and subsequent examples show the use of the same two oxides but with butylene oxide being used first as shown on the table.

Example 73F and subsequent examples relate to the use TABLE IX Composition before Composition at end Oxides Oxides Molal ratio No. 080, Catas01- Oata- Sol- Theo. Ex. OSC, lyst, vent, S0, lyst, vent, EtO PrO BuO mol. No. lbs. EtO, PrO, 13110, lbs. lbs. lbs. EtO, PrO, B110, lbs. lbs. to oxyto oxyto oxywt.

lbs. lbs. lbs. lbs. lbs. lbs. alkyl. alkyl. alkyl.

suscept. suscept. suscept. compd. compd. compd.

1E... 1D 18.70 1.0 is. 70 1s. 70 9.35 1.0 18.70 42. 5,610 213... 1D 18.70 9. 35 1.0 18, 70 13. 70 18.70 1.0 18.70 85.0 7,480 $11.. 11 18.70 18.70 1.0 18.70 18.70 28.05 1.0 18. 70 127. 5 9, 350 4E... 1D 18.70 28.05 1.0 18.70 18.70 37. 4 1.0 18.70 170.0 11,220 1.0 18. 70 18.70 16. 75 1. 0 18.70 212. 5 13.090 1.0 18.70 18.70 56. 1.0 18. 70 255. 0 14. 960 1.0 18. 25 18. 9.1 1.0 18. 41. 3 5, 460 1. O 18. 25 18.20 18. 2 1. 0 18.25 82.6 7,280 1. O 18. 25 18.20 27. 3 1.0 18. 25 123. 9 9,100 1.0 18. 25 13. 20 36. 4 1.0 18.25 165. 2 10,920 1.0 18.25 18. 20 45. 5 1.0 18.25 206. 5 12, 740 1.0 18.25 18.20 72. 8 1.0 18. 25 330. 4 18,200 1.0 19. 80 19.70 5. 0 1.0 19. 80 22. 7 4, 940 1.0 19. 80 19.70 15.0 1.0 19.80 68.1 6, 940 1. 0 19. 80 19.70 20. 0 1.0 19. 80 90. 8 7, 910 1.0 19. 80 19.70 30. 0 1.0 19. 80 136.2 9, 940 1.0 19. 80 19.70 45. 0 1. 0 19. 80 204. 3 12, 940 1. 0 19. 8O 19. 60. 0 l. 0 19. 80 272. 4 15, 940 1. 5 18. 70 18.70 1. 5 18.70 7, 480 1. 5 18. 70 1. 5 18. 70 11,220 1. 5 18.70 1. 5 18.70 14,960 1. 5 18. 70 1. 5 18.70 16,690 1. 5 1g, 70 1. 5 18.70 18,560 1. 5 18. 70 1.5 18. 70 20,430 1, 5 13, 5 1. 5 18. 25 7, 240 1. 5 18.25 1. 5 18. 25 10, 840 1. 5 18. 25 l. 5 18. 25 14, 440 1. 5 18. 25 1. 5 18. 25 18, 040 1. 5 18. 25 1. 5 18.25 18. 940 1. 5 13. 25 1. 5 18.25 25, 240 l. 5 19. 8O 1. 5 19. 80 7, 880 1. 5 19. 80 l. 5 19. 80 820 1. 5 19, so 1. 5 19.80 15, 760 1. 5 19. 80 1. 5 19. 80 19, 700 1.5 19. 80 1. 5 19. 80 23, 640 1. 5 19. 80 1. 5 19. 80 25, 610 1. 5 18. 70 1. 5 51. 9 7, 480 1. 5 18.70 1. 5 103. 8 11, 220 1. 5 18. 70 1. 5 129. 13. 090 1. 5 18. 70 18. 1. 5 155. 7 14, 950 1. 5 18 70 18. 1. 5 181. 65 16, 830 1. 5 18. 70 1. 5 207.6 18,700 1. 5 18. 25 18. 1. 5 50. 5 7, 280 is. 2 1. 5 13, 5 18. 1. 5 101.0 10, 920 36. 4 1. 5 18. 25 18. 1. 5 14, 560 54. 6 1. 5 13. 25 18. 1. 5 16, 380 63. 7 1. 5 18.25 18. 1. 5 18, 200 72. 8 1. 5 18. 25 18. 1. 5 20, 020 1. 5 19. 19. 1 7, 880 19. 7 1. 5 19.80 10. 1. 5 11,820 39. 4 1. 5 19. 80 10. 1. 5 15, 760 59. 1 1. 5 19.80 19. 1. 5 17, 880 68. 1. 5 19. 8O 19. l. 5 19. 300 78.80 1. 5 19. 80 10. 1. 5 19. 80 21, 770

of propylene oxide and butylene oxide. Examples beginning with 1G, Table XI, particularly 2G, 36, etc., show the use of all three oxides so there are no blanks as in the first step of each stage where one oxide is missing. It is not believed any further explanation need be offered in regard to Table XI.

As previously pointed out certain initial runs using one oxide only, or in some instances two oxides had to be duplicated when used as intermediates subsequently for further reaction. It would be confusing to refer to too much detail in these various tables for the reason that all pertinent data appears and the tables are essentially selfexplanatory.

Reference to solvent and amount of alkali at any point takes into consideration the solvent from the previous step and the alkali left from this step. As previously pointed out, Tables X11, XIII and XIV give operating data in connection with the entire series, comparable to what has been said in regard to Examples 1E through 6E.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired, the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i.e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

The same would be true in regard to a mixture of ethylene oxide and butylene oxide, or butylene oxide and propylene oxide.

The colors of the products usually vary from a reddish amber tint to a definitely red, amber and to a straw or light straw color. The reason is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent. Oxyalkyla- Theo. mol. wt.

8 1 2 3 .t. 555555 ow mwm. 77777755555544 4444060066000000777777 0k 0 m Own 0 09 0 LL L L L L O 0 00m Own 7 T 7 7 7 7 LL L LL LA ATA A A 4 B S 222222555555000000000000000000555555 O au 11111111111111.1111222222111111 S 1 t d 555555 5 5 5 5 24 0 m WWW 777777444444000000257025010102804311 1 .1 0k 6 m 5 5 5 5 .afiomomomemomomQuJl Z 4 5 0 L 2% 1 Z 7 3 oak- 5 3 7 55 m P 222222%4444 400000030n 209307902630300 O aw 222222 22222222222 111 11 12233 M 8w 5 5 5 5 5 555555 OW WW 005050639625855610000000222222000000 t k 0 m 7 12 57 00L 1 2 5 010 7 4 2 um 0 00 0 00 1.3 3 033 0 09099 E 1 13482724086048024 777777000000777777 aw 11 12 111 11111111111111.1111 555555 555555 7777772222 2888888777777222222888888 S01- vent, lbs.

Catalyst,

Composition at end Oxides EtO, PrO, BuO, lbs.

lbs.

Kerosene Insoluble n. Insoluble.

soluble D0 Insoluble TABLE X1 080, lbs.

Solvent, lbs.

Solubility Xylene S0lublo Insoluble.

88S8880o0c8888999999800888888888809999 11.1111111111111111111.111111111111111.

Catalyst,

Water Insoluble-..

Emulsifiable d0 Oxides PrO, BuO, lbs.

lbs.

TABLE XII Time, hrs

Composition before Et 0 lbs.

Max pres, p. s. i.

OSC, lbs.

Max. temp C.

080, Ex. No.

Ex. N0.

Ex. N0.

8E 9E v 10E 41E 42E 13E 

1. A 3-STEP MANUFACTURING METHOD INVOLING (1) CONDENSATION; (2) OXYALKYLATION WITH A POLYEPOXIDE CONTAINING AT LEAST TWO 1,2-EPOXY RINGS; AND (3) OXYALKYLATION WITH AN ALPHA-BETA MONOEPOXIDE; SAID FIRST MANUFACTURING PROCESS BEING A STEP OF (A) CONDENSING (A) FUSIBLE, NON-OXYGENTED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 